Orange phenylazoazobenzene acid dye

ABSTRACT

Orange phenylazoazobenzene acid dyes which have good application and excellent lightfastness properties on deep-dyeing nylon fibers and good non-staining properties on acid-modified nylon fibers.

United States Patent [191 Speck [4 1 Sept. 16, 19 75 ORANGE PHENYLAZOAZOBENZENE ACID DYE [75] Inventor: Stanley B. Speck, Wilmington, Del.

[73] Assignee: E. I. Du Pont de Nemdurs and Company, Wilmington, Del.

22 Filed: July 2, 1973 21 Appl. No.2 375,944

Related US. Application Data [62] Division of Ser. No. 301,81 1, Oct. 30, 1972, Pat. No.

[52] US. Cl. 260/186; 8/26; 8/27; 8/41 B; 8/89; 260/163; 260/177; 260/178;

[51] Int. Cl. C0913 31/06; D06P 3/24 [58] Field of Search 260/174, 177, 178, 184, 260/186, 187, 185, 191

Primary Examiner-Floyd D.. Higel [57] ABSTRACT Orange phenylazoazobenzene acid dyes which have good application and excellent lightfastness properties on deep-dyeing nylon fibers and good non-staining properties on acid-modified nylon fibers.

5 Claims, N0 Drawings ORANGE PHENYLAZOAZOBENZENE ACID DYE CROSS-REFERENCES TO RELATED APPLICATION BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to aqueous, dye baths containing mixtures of compatible acid dyes, some of which are novel, which are useful for dyeing deep-dyeing nylon fibers.

2. Description of the Prior Art Nylon styling yarns have increased in commmercial importance in recent years because of their physical and chemical durability and their multicolor dyeability. Such properties are especially desirable in carpet fibers. Nylon styling yarns generally consist of fibers of an acid-modified (anionic) nylon containing sulfonic acid groups which make the fibers receptive to basic dyes and two or more unmodified nylons which differ in their amine end group content and hence their receptivity to acid dyes. Such yarns are known to be dyeable both by exhaust and continuous methods. In the carpet industry such yarns in the form of bulked continuous filament (BCF) yarns may be dyed with combinations of basic, acid and disperse dyes. Basic (cationic) dyes which have good application and fastness properties on acid-modified nylon and which reserve, that is, produce little or no stain on, unmodified nylons under the neutral to weakly acidic conditions used to dye nylon styling yarns are readily available commercially. Also readily available are monosulfonated acid dyes which reserve acid-modified nylon while producing light to heavy shades of good fastness properties on unmodified nylons, the shade depending on the amine end group content of the unmodified nylon. Light-dyeing nylons are generally recognized in the art as having an amine end group content of 25 gram equivalents or less per million grams of the polymer; deep-dyeing nylons generally contain 70 or more gram equivalents of free amine end groups per million grams of the polymer; and medium-dyeing nylons contain an intermediate number of amine end groups, generally about 40-50 gram equivalents per million grams of the polymer. Disperse dyes can be used to dye acid-modified and all types of unmodified nylon fibers to the same degree. It can be seen, therefore, that a combination of basic, acid and disperse dyes can be employed to achieve a broad range of color effects on nylon styling yarns. This range can be broadened by using disulfonated or monosulfonated/monocarboxylated dyes instead of the aforesaid monosulfonated dyes. Such dyes have considerably more affinity for deep-dyeing nylons and pro duce a much greater shade contrast between these fibers and light-and medium-dyeing nylons than is possible with monosulfonated dyes. In practice, the selection of dyes containing two functional acidic groups for use on nylon styling yarns is extremely difficult. Although such dyes may have adequate buildup and lightfastness on deep-dyeing nylon is self-shades and show good reserve of light-dyeing and acid-modified nylons, they may exhibit a blocking action on each other when applied from the same dye bath. In other words, one diacidic dye may preferentially dye deep-dyeing nylon and prevent another such dye from exhausting completely onto the substrate, in which case unlevel dyeings may be produced and the anticipated mixed shade may not be obtained. In the continuous dyeing of tufted nylon styling yarn carpeting, the use of diacidic dyes which exhibit the incompatibility described above may result in tippy dyeings (tippinesslwherein the top of the tuft is different in shade from the bottom;

SUMMARY OF THE INVENTION It is an object of this invention to provide aqueous dye baths containing compatible yellow, orange, red, blue, blue-green or green acid dyes which are useful for dyeing deep-dyeing nylon fibers while exhibiting little or no blocking action upon each other. It is a further object to provide dye baths containing such dyes which exhibit good application and fastness properties on deep-dyeing nylon fibers and excellent reserve of acidmodified nylon fibers. It is a still further object to provide dyes which exhibit excellent shade contrast on light-, mediumand deep-dyeing nylons. In summary, the invention relates to aqueous dye baths which are useful in dyeing deep-dyeing nylon fibers, which dye baths have a pH of 4-7 and contain dyes, some of which are novel, selected from 2-3 of the following groups, wherein M in each group is a cationselected from H, Li, Na, K, NH di(hydroxy-C ;,alkyl)- ammonium and tri(hydroxy-C alkyl)ammonium:

l. A yellow dye of the structure R is C] and R is $0 M,

b. Ar is Q CO M R is Cl and R is $0 M. or

0. Ar is R is M and R is H;

2. An orange dye of the structure @N-an o II=N-@OCHQTHOH $03M g R wherein R is H, CH or can;

3. A novel orange dye of the structure 5. A blue dye of the structure wherein R is $0 M and R is H, CH OCH or C1, or R is p-NHCOCO H and R is H; and

6. A blue-green to green dye of the structure x 0 NH Q X 0 NH R wherein X is H or OH, R, is H and R is C H C H OCH or OC H or R is CH; and R is CH, or OCH Generally no more than one dye is selected from each of the 2-3 groups since there is little shade varia tion Within a group.

DETAILED DESCRIPTION OF THE INVENTION The invention, as already stated, relates to aqueous dye baths having a pH of 4-7, which dye baths contain a mixture of acid dyes, some of which are novel, se-

lected from 23 of the aforesaid six dye groups. Following is a discussion of each of the six groups.

The yellow monoazo dyes are, for the most part, known in the art and are preparable by conventional diazotization and coupling techniques employing as the diazo compound 5-chloroorthanilic acid, 5-

.chloroanthranilic acid or 2-naphthylamine-l-sulfonic acid and as the coupling compound l-(2,5-dichloro-4- sulfophenyl)-3-methylpyrazol-5-one or l-(2-chloro-5- sulfophenyl )-3-methylpyrazol-5-one.

The first group of orange disazo dyes can be prepared by adding ethylene-, propyleneor butylene oxide to the disazo dye obtained, by conventional diazotization and coupling techniques, from metanilic acid, l-naphthylamine-6-sulfonic acid and phenol. The addition reaction is carried out under alkaline conditions at an elevated temperature, preferably l()()C. Because of the low boiling points of ethylene oxide and propylene oxide, either is best reacted with the disazo dye in an autoclave. The preferred basic catalyst is lithium or sodium hydroxide in an amount up to about 20 mole of the disazo compound. Significantly more base than this causes an undue amount of deactivation of the epoxide by ring opening. A oneto three-fold molar excess of the epoxide over the disazo dye is desir able to ensure a high yield of the product. Precipitation of the dye can be achieved, if necessary, by salting the aqueous or aqueous organic reaction mixture. The dye is then isolated by filtration. Experiment 1 provided hereafter illustrates the preparation of one such orange dye.

The second group of orange disazo dyes includes novel dyes which can be prepared by coupling diazotized 4-aminoazobenzene-3,4-disulfonic acid to a p-C, ,,alkylphenol under alkaline conditions employing known procedures. Such dyes wherein M is Na and R is C alkyl (in the formulapreviously given) exhibit the following spectral data:

Ahsorptivity Wavelength of Maximum Ahsorhancc R. (liters/gram/cm.) (mu) C H;,' 50.0 365 t-butyl 42.2 365 t-amyl 32.8 367 t-octyl 9.] 368 The blue anthraquinone dyes can be prepared by conventional procedures. Two such dyes can be pre pared by condensing 1-amino-4-bromoanthraquinone- 2-sulfonic acid (Bromamine acid) with metanilic acid or oxalic acid mono4-aminoanilide. Other such blue dyes can be prepared by condensing Bromamine acid in known manner with aniline, 0-, mor p-toluidine, o-, mor p-anisidine, or o-, mor p-chloroaniline, followed by sulfonation of the phenyl ring. Experiment 3 provided hereafter illustrates the preparation of one such blue dye.

The blue-green to green anthraquinone dyes can be prepared by Well known bis condensation procedures employing l ,4-dihydroxyanthraquinone, l,4 dichloro(or dibromo)anthraquinone or l,4,5,8- tetrahydroxyanthraquinone and a suitable aniline derivative, the his condensation product then being disulfonated in a conventional manner. Suitable aniline de rivatives include 2,4xylidine, 4-ethylaniline, 4- propylaniline, 2methyl-4-anisidine, 4-anisidine and 4- phenetidine.

For economic reasons, the aforesaid acid dyes are usually isolated as the sodium salts. However, it is sometimes advantageous to prepare the acid dye as the lithium, potassium, ammonium, di(hydroxy-C alkyl- )ammonium or tri(hydroxy-C alkyl)ammonium salt, or a mixture of such salts, in order to improve its water solubility. The salt can be formed during the preparation of the dye. Alternatively, the sodium salt ofthe dye can be dissolved in water and acidified with a mineral acid to give the free acid form of the dye which can then be isolated by filtration or by extraction into a suitable solvent, such as n-butanol, followed by evaporation to dryness. The free acid can then be converted to the desired salt by titration in water against a suitable base, such as lithium, potassium or ammonium hydroxide, or an alkanolamine such as diethanolamine, diisopropanolamine or triethanolamine, or a mixture of such amines.

The aforesaid acid dyes employed in the aqueous dye baths of this invention include representatives of the three primary colors red, yellow and blue and can, therefore, be mixed to produce a complete range of colors. Since acid dyes form ionic bonds with basic groups on the substrate, the aforesaid dyes have utility on any polycarboxamide fiber containing a sufficiently high concentration of amine end groups, including the commercially available deep-dyeing and ultra-deepdyeing nylons which contain 70l2() gram equivalents of amine end groups per million grams of the polymer. The most common of these deep-dyeing nylons is poly(hexamethylene adipamide).

The dye baths of this invention can be applied to nylon styling yarns by batch or continuous methods. The most important end use for such yarns is carpeting although they are employed in other end uses, such as upholstery or accent rugs (throw rugs). The batch dyeing of carpets is normally carried out in a beck; upholstery is commonly dyed in jigs and accent or throw rugs, in paddle machines. The dyeing procedure is essentially the same in each case. The continuous dyeing of nylon carpeting is carried out in equipment such as the commercially available Kusters machine described in Example 1. Whether applied by batch or continuous procedures, the dyes employed in the dye baths of this invention produce uniform shades on deep-dyeing nylon fibers and uniform on-tone but much lighter shades on lightand medium-dyeing nylons, if present. Little or no tippiness is observed on tufted nylon carpeting, the tufts being dyed a uniform shade from top to bottom. Acid-modified nylon is completely reserved by the dyes employed herein.

Monosulfonated, disperse and basic dyes also can be present in the dye baths of this invention. Coprecipitation of the acid and. basic dyes can be pre vented by means of various agents known in the art, for example, an amphoteric agent such as the sulfobetaine having the formula wherein R is alkyl of 7-l7 carbon atoms and m, n and the sum of m and n are 0-3. The dyeing of nylon styling yarns is generally carried out at a pH of 4-7, depending on the particular procedure and the types of dyes present in the dye bath. Hence, the dye baths of this invention are most desirably maintained at a pH of 4-7.

Representative syntheses of the dyes which are used in the above-described dye baths are included in the following experiments wherein all parts are by weight unless otherwise noted.

EXPERIMENT 1 Preparation of Orange Disazo Dye Metanilic acid was diazotized by a conventional procedure and coupled under acidic conditions to l-naphthylamine-o-sulfonic acid. A slurry of 60.2 parts of the resulting monoazo amine in 500 parts of water and 37.5 parts of ION-hydrochloric acid was cooled to 10C. and 18.3 parts of SN-sodium nitrite were added portion-wise. After the mixture was stirred for 30 minutes, excess nitrite was destroyed with sulfamic acid and the diazo solution was added over a l.5-hour period to a solution of 5.9 parts of phenol in 250 parts of water containing 40 parts of sodium carbonate and 53 parts of 30% sodium hydroxide solution which had been precooled to 10C. The reaction mixture was stirred for 2 hours, the temperature being allowed to rise to 25C. The pH was adjusted to 7.3 with hydrochloric acid and 165 parts of sodium chloride were added with agitation. The resulting precipitate was isolated by filtration and dried, yielding 37.1 parts of the crude disazo dye. The solids were slurried in 192 parts of water and parts of ethylene glycol monoethyl ether. The pH was adjusted to 9.5 with sodium hydroxide and the mixture was heated in an autoclave with 5.3 parts of ethylene oxide at C. for 14 hours. The mixture was cooled and the product was collected on a filter, washed with I071 aqueous sodium chloride solution and dried. The yield of orange dye was 27.2 parts; the dye exhibited an absorptivity (a m) f 48.2 liters/- gram/cm. (1./g./cm.) at a wavelength (A of 435 mu. It had the structure given above wherein R is H and M is Na.

EXPERIMENT 2 Preparation of Novel Orange Disazo Dyes a. 4-Aminoazobenzene-4-sodium sulfonate (9 parts) was added in 2 hours with stirring to a mixture of 20.75 parts of 7? sulfuric acid and 0.9 part of 65% oleum 100% sulfuric acid containing 65 weight After :he reaction mixture had been stirred for an additional ).5 hour, it was cooled to 17C. and 12.7 parts of 65% )leum were added, the temperature being maintained it 17 1 2C. The mixture was stirred at ambient tem- )erature for hours and then drowned in 51 parts of vater, the temperature being kept below 40C. The nass was then cooled to 5C. and stirred for 0.5 hour. [he solids were isolated by filtration. The wet cake was .lurried in 160 parts of water and dissolved by heating lowly to 55C. with agitation. After 15.8 parts of con- :entrated hydrochloric acid had been added, the mixure was allowed to cool to room temperature with oc- :asional agitation. It was then cooled externally to 0C. and stirred at this temperature for 24 hours. The olids were then filtered off, washed with 16 parts of 1% hydrochloric acid and dried. A yield of 5.8 parts of 'ellow product was obtained.

b. A slurry of 2.5 parts of the solids from (a) in 12 arts of water and 2.84 parts of concentrated hydro- :hloric acid was cooled to 5C. and treated portionvisewith 1.88 parts of SN-sodium nitrite. After the nixture had been stirred for 0.5 hour at about 5C., ex- :ess nitrite was destroyed with sulfamic acid and the :old diazo preparation was added dropwise to a rapidly tirred solution of 1.12 parts of p-t-butylphenol, 24.5 arts of water, 1 1 parts of ethanol, 28 parts of sodium lydroxide and 2.1 parts of anhydrous sodium carbon- .te at 30C. The pH of the reaction mixture was maintained at 9 by periodically adding aqueous caustic oda. When addition of the diazo compound was com llete, the mixture was stirred for 0.5 hour at 2530C, nd the solids were isolated by filtration, washed with 0% aqueous sodium chloride and dried. A yield of ..25 parts of dye was obtained; the dye exhibited an aborptivity of 42.2 liters/gram/cm. at a wavelength \max) of Ill/.L.

c. When (b) was repeated three times except that p-tutylphenol was replaced with an equimolar amount of -cresol, p-t-amylphenol and p-t-octylphenol, respecively, orange dyes were obtained having the spectral haracteristics previously given.

EXPERIMENT 3 Preparation of Blue Anthraquinone Dye The pH ofa mixture of 24.2 parts of Bromamine acid nd 20.6 parts of sodium metanilate in 100 parts of ater was'adjusted to 7 with hydrochloric acid. Next 'ere added 7 parts of sodium carbonate, 10.2 parts of Jdium bicarbonate, 1.35 parts of cuprous chloride and 40 parts of water. The mixture was stirred at O80C. for 12 hours. The reaction mixture was claried by filtration and the product was salted out of soluon with sodium chloride. The dye was isolated by filation, washed with 2572 aqueous sodium chloride soltion and dried. A yield of 32.8 parts of chromatoraphically pure blue dye was obtained. It had the ructure given above wherein R is m-sulfo, R is H and l is Na.

In order to illustrate the utility of the dye baths of this ivention, the examples given below describe their ap- I lication, in the absence of other dyes, to nylon test irpeting which consists mainly of various types of ylon tufted in discreet bands onto ajute backing. The .entification of the dyes employed in the dye baths of ie examples corresponds to the descriptions of the six cups of structures recited above, In all cases, M is Na.

Orange Dye 2 Orange Dye 3(a) Orange Dye 3(b) Orange Dye 3(c) Orange Dye 3(d) Dye 2 where R:, is H Dye 3 where R is CH Dye 3 where R is t-butyl Dye 3 where R, is t-amyl Dye 3 where R, is t-octyl Red Dye 4(a) I Dye 4 where R;, is C,,H,,CONH and R is H Red Dye 4(b) I Dye 4 where R is H and R is C,,H CONH Blue Dye 5(a) I Dye 5 where R is m-sulfo and R is H Blue Dye 5(b) 2 Dye 5 where R is p-NHCOCO H and R,- is H Blue Dye 5(e) Z Dye 5 where R is o-sulfo and R is p-CH Blue Dye 5(d) I Dye 5 where R,; is p-sulfo and R is H Blue Dye 5(e) I Dye 5 where R is p-sulfo and R is 0OCH;, Blue Dye 5(f) I Dye 5 where R, is m-sulfo and R is p-Cl Blue-green Dye I Dye 6 where R and R are CH $0 M is ortho and X is H I Dye 6 where R and R are CH S0,,M

is ortho and X is OH.

6(a) Green Dye 6( b) EXAMPLE 1 Yellow Dye 1(0) 1 g./l. Red Dye 4(a) l g./l. Blue Dye 5(a) l g./l. an organic alcohol extended with 0.25 g./l.

ethylene oxide a sulfated polyglycol ether 1.25 g./l. a purified natural gum thickener 2 g./l. acetic acid 3 g./l. monosodium phosphate to adjust the pH to 5.

Pickup was about 400%. The carpeting was then run through a steamer at C, the dwell time being 8 minutes. Finally, the carpeting was rinsed thoroughly and dried. A uniform deep brown shade was produced; the tufts displayed no tippiness.

b. The procedure described in (a) was repeated on 7-inch wide, jute-backed, tufted carpeting consisting of bands, each two tufts wide, of T-847 (deep-dyeing), T-846 (mediumdyeing), T-845 (light-dyeing) and T-844 (acid-modified) nylon, the pattern being repeated along the length of the carpet. The bands of deep-dyeing nylon were dyed a deep brown shade; the medium-dyeing nylon bands were much lighter in shade but on-tone vs. the deep-dyeing nylon; the lightdyeing nylon bands were dyed a very light brown shade; the acid-modified nylon bands were completely reserved.

EXAMPLE 2 The procedure of Examples 1(a and 1(1)) were repeated except that the following dye mixture was used in the dye bath:

Yellow Dye l(c) 4.5 g./l. Red Dye 4(b) 1 g./l. Blue Dye 5(a) 3 g./l.

A deep green shade was produced on the deep-dyeing nylon. No tippiness or unlevelness was apparent. A medium, on-tone shade was produced on the mediumdyeing nylon and a very light green shade, on the lightan organic alcohol extended with 8 g./l.

ethylene oxide a sulfutcd polyglycol ether 4 g./l. citric acid 80 g./l.

sodium hydroxide dyeing nylon. The acid-modified nylon was completely 5 reserved.

25 Parts of the carpeting described above were dipped EXAMPLE 3 into the bath at room temperature and removed. A

. W The procedures of Examples 1(a) and 1(b) were remlxtur; of f :2 fi g i z the r w peated using the following dye mlxture: 10 a Su sequeil y ea 6 o e 6 came ng a reintroduced into the bath for 5 minutes, removed and rinsed with water. The pH of the bath was then dropped Orange Dye 2 0.7 g./l. to 3 and an undyed-sample of deep-dyeing nylon carg g 2 3 -flpeting was added to the boiling bath and left until the y g 5 dye remalnlng m the bath was completely exhausted The de r e of leve ness and reserve ob A deep brown shade, mcuh redder than that obtained S g d d C r b the above m in Example 1, was produced on the deep-dyeing nylon. 'g on F A: ny p 1 y l ith g w No tlpplness was observed and the levelness of shade i a E 0 F a g z z g e Ll was excellent. As with the previous examples, the shade ts o ame y a F d Du g All the dye combinations described in thefollowlng variations on the medlumand light-dyeing nylons and 20 r table exhausted well and produced deep nontlppy reserve of the acid-modified nylon were excellent.

shades on the deep-dyeing nylon band and light to very EXAMPL 4 2 light shades on the light-dyeing nylon band. The acidmodified nylon was unstained. Levelness of shade on In these examples pieces of p yp py n 25 the deep-dyeing nylon band was rated by the following nylon carpeting were pot dyed with various dye combil nations. The carpeting was 4 inches wide and consisted 5 little no unlevelness of three bands, one each of deep-dyeing, light-dyeing 4 slight unlevelness and acid-modified nylon. Each band was tufts long. 3 i bl unlevelness L000 Parts of an aqueous bath were prepared so as to 30 2 id bl unlevelness contain: 1 much unlevelness Example Dyes Levelness on Deep-Dyeing Number (7: on Weight of Fiber) Shade Nylon Band 4 Blue Dye 5(b) (0.1571) Violet 4 Red D e 4(a) 0.075% 5 Blue Dye 5(e) (0.l571) Violet 5 Red Dye 4(a) (0.07571) 6 Blue Dye 5(a) (0.271) Green 5 Yellow Dye [(b) (0.271) 7 Blue Dye 5(a) (0271) Green 4 Yellow Dye 1(a) (0.2371) 8 Blue Dye 5(d) (0.l771) Green 5 Yellow Dye 1(b) (0.271) 9 Blue Dye 5(d) (0.1771) Green 5 Yellow Dye l(u) (0.2371) 10 Blue Dye 5(e) (01771) Green 5 Yellow Dye l(b) 0.2% II Blue Dye 5(e) (0.177?) Green 4 Yellow Dye [(21) (0.2371) 12 Blue Dye 5(f) (0.2%) Green 5 Yellow Dye 1(h) 0.20% 13 Blue Dye 5(f) (0.271) Green 5 Yellow Dye 1(a) (0.2371) 14 Blue Dye 5(c) (0271) Brown 5 Red Dye 4(a) (0.271) Yellow Dye l(c) (0.271) 15 Blue-green Dye 6(a) (0.0771) Brown 5 Red Dye 4(a) (0.129?) Yellow Dye l(c) (0.171) 16 Green Dye 6(h) (0.0471) Brown 5 Red Dyc 4(a) (0.1571) Yellow Dye l(c) (0.0571) 17 Orange Dye 3(b) (0.0571) Brown 5 Red Dye 4(a) (0.171) Blue Dye 5(a) (0.171) 18 Orange Dye 3(h) (0.0571) Brown 5 Red Dye 4(h) (0.l71) Blue Dye 5(a) (0.l71) l9 Orange Dye 3(a) (0.0571) Brown 5 Red Dye 4(a) (0.1571) Blue Dye 5(a) (0.171) 20 Orange Dye 3(0) (0.0771) Brown 5 Red Dye 4(2)) (0157) Blue Dye 5(a) (().I71) 21 Orange Dye 3(d) (0.2271) Brown 5 Red Dye 4(a) (0.1571) Blue Dye 5(a) (0.l71)

to adjust the pH to EXAMPLE 22 25 Parts of the carpeting described in Example 4 were heated (beck dyeing) at 99C. for 1 hour in 1,000 )arts of an aqueous bath containing:

ellow Dye 1(0) 0.04 part led Dye 4(a) 0.03 part iluc Dye 5(a) 0.04 part :thylencdiaminetctraacctic acid, 2.5 parts sodium salt :itric acid 4 parts odium hydroxide to adjust the pH to 5.8.

Fhe deep-dyeing nylon was dyed a deep, uniform, nonippy brown shade. The light-dyeing nylon was almost :ompletely reserved The acid-modified nylon was untained. When the above procedure was repeated at pH |.5, the light-dyeing nylon was practically unstained.

EXAMPLE 23 a. A sample of jute-backed nylon shag styling yarn arpeting containing deep-dyeing, light-dyeing and cid-modified nylon strands was run through a wet-out ath at 27C. containing 1.5 grams per liter of an oranic alcohol extended with ethylene oxide and 0.2 ram per liter of ethylenediaminetetraacetic acid, soium salt. The carpeting was then treated with an aqueus dye bath at 27C. containing:

Yellow Dye l(c) 0.6 g./l. Red Dye 4(a) (H4 g-ll- Blue Dye 5(a) 0.3 g./l. an organic alcohol extended with ethylene oxide 0.05 g./l. a sulfated polyglycol ether 0.] g./|. a purified natural gum thickener 2.5 g./l.

monosodium phosphate to adjust the pH wherein M is a cation selected from H, Li, Na, K, NH di(hydroxy-C alkyl)ammonium and tri(hydroxy-C ;,alkyl)ammonium and R is C alkyl.

2. The orange dye of claim 1 wherein M is Na and R is CH 3. The orange dye of claim 1 wherein M is Na and R is t-butyl.

4. The orange dye of claim 1 wherein M is Na and R is t-amyl.

5. The orange dye of claim 1 wherein M is Na and R is t-octyl. 

1. THE ORANGE DYE OF THE STRUCTURE
 2. The orange dye of claim 1 wherein M is Na and R4 is CH3.
 3. The orange dye of claim 1 wherein M is Na and R4 is t-butyl.
 4. The orange dye of claim 1 wherein M is Na and R4 is t-amyl.
 5. The orange dye of claim 1 wherein M is Na and R4 is t-octyl. 